Dentifrices



, Patented Oct. 11, 1960 DENTIFRICES Michael Gabriel Buonocore, Rochester, N.Y., and Martin Kuna, Wesflield, N.J.,. assignors to Bristol-Myers Company, New York, N.Y., a corporation of Delaware Filed June 18, 1956, Ser. No. 591,808 12 Claims. c1. 167-93) No Drawing.

This invention relates to a dentifrice, and more particularly to a dentifrice in paste, powder or liquid form, which tends to reduce the normal susceptibility of the teeth to attack from acid.

It is generally accepted that dental caries result at least partially from the acids formed by microorganisms in the mouth in the course of their metabolism. These acids, when in contact with the teeth, attack the enamel of the teeth, dissolving the enamel and result in tooth decay. A great deal of research effort has been devoted to find a means of protecting the teeth against the attack of these acids. Numerous proposals have been advanced to overcome the problem. Those skilled in the dentifrice art are familiar with these proposals. One proposal was the use of basic ammonium salts in a dentifrice. These were known as the ammoniated dentifrices. Another was the use of chlorophyll in a dentifrice. Another was the incorporation of a so-called anti-enzyme, such as sodium lauryl sulfate, into a dentifrice. While some of these proposals have given indications of being helpful, none of them has provided satisfactory protection of the teeth against the ravages of acids, such as are formed in the mouth.

It is an object of the present invention to provide an improved dentifrice having the property of reducing the normal susceptibility of the teeth to acid attack.

It is another object of the present invention to incor-, porate in'a dentifrice an agent afiording protection to the teeth enamel against acid attack and resisting calculus formation on the teeth.

-Other objects will be apparent to those skilled in the from reading the description which follows. i

i The present invention is predicated upon the discovery that a dentifrice containing as an essential ingredient certain organic phosphates and their water-soluble salts will reduce the dissolving action of acids on dental enamel. Such a dentifrice also retards calculus formation and other deposits on the surface of the teeth.

These organic phosphates are mono-, diand tri-alkyl or-aralkyl esters of phosphoric acid and their watersoluble salts. These esters are desirably esters of orthophosphoric acid of the formula:

wherein R is an aralkyl group or alkyl group containing at least 7 carbon atoms, and preferably not more than 24 carbon atoms, with groups containing from 12 to 16 carbon atoms providing best results, or an alkyl group containing at least 1 carbon atom when at least one of R and R is also an alkyl or aralkyl group;

R and R are hydrogen, an alkyl or aralkyl group containing at least 1 carbon atom, preferably not more than 24 carbon atoms and more preferably from 12 to 16 carbon atoms, or an alkali-metal or ammonium ion.

The organic phosphates and their-water-soluble salts are known chemical compounds and per se do not constitute a part of this invention. These esters are available commercially and may be produced by several known methods, including the reaction between an aliphatic or aralkyl alcohol and phosphorus pentoxide or phosphorus oxychloride. One such method is described in U.S. Patent No. 2,586,897 of W. H. Woodstock. Among the preferred organic phosphates for employment in the dentifrices of the invention are: tri-benzyl orthophosphate, mono-sodium-di-normal-butyl orthophosphate,

mono-potassiurn-di-Z-ethylhexyl orthophosphate, tri-lauryl orthophosphate, mono-sodium-di-methyl orthophosphate, mono-sodium-di-normal-octyl orthophosphate, di-sodiurnmono-stearyl orthophosphate, mono-sodium-di-stearyl orthophosphate, di-sodium-mono-lauryl orthophosphate, mono-sodium-di-lauryl orthophosphate, di-lauryl orthophosphoric acid, etc., and mixtures of them. The sodium ion in the salts may be replaced with the ammonium ion or other alkali-metal ion to form such salts as mono- :ammonium-di-lauryl orthophosphate, di-potassium-monostearyl orthophosphate, etc.

While the concentration of the organic phosphate in the dentifrice may vary, best results are obtained where the organic phosphate constitutes between about 0.05% and 2.0%, and preferably between 1.0% and 1.8%, by weight of the, total dentrifrice composition. Below 0.05% the organic phosphate may be ineffective, and

above 2.0% it may not be utilized efiiciently.

Where the dentrifrice is a paste or powder it is desirable to incorporate into the dentifrice a solid polishing agent, such as dicalcium phosphate, calcium pyrophosphate, tricalcium phosphate or powdered chalk (calcium carbonate), etc, Non-calciuni-containing polishing agents, such as aluminum oxide, titanium dioxide, ground pumice, powdered nylon, etc., may be employed.

In addition to the organic phosphate and polishing agent (when desired), the dentifrice can contain as optional ingredients a soap or synthetic detergent as a surface tension depressant. Soaps of high molecular weight fatty acids, including, for example, sodium and potassium soaps of myristic, stearic and palmitic acids and the fatty acid mixtures of palm oil and coconut oil, as well as diglycol laurate, diglycol stearate and glycostearine, can be employed. Typical synthetic detergents include the alkyl sulfates and sulfonates having alkyl groups of from about 8 to about 18 carbon atoms, such as sodium lauryl sulfate, the sulfated fatty alcohols derived from coconut oil and palm oil, sodium cetyl sulfate, sulfated sperm oil fatty alcohols and sodium oelyl sulfate, salts of fatty acid amides of taurines (the Igepons such :as sodium palrnitic methyl tauride, sulfated glycerides, such as oleyl, stearic,

' palmitic and ricinoleic glycerides, usually in the form of mixed glycerides and sulfonated hydrocarbons having from 8 to 20'carbon atoms, such as sulfonated decanes, dodecanes and octadecanes. Particularly good results are obtained with Tweens, such as Tween 20 which is the polyoxyethylene derivative of sorbitan, and Atlas 6-2160 which is the polyoxyethylene derivative of mannitan. Another type is the Drucals, such as sodium lauroylisethionate. Other optional conventional components of a dentifrice which may be present include flavoring materials, such as the flavoring oils (peppermint oil, etc); sweeteners, such as sucrose, glucose, saccharin and sodium cyclamate, and harmless coloring materials, in proportions to give any desired taste or flavor or other effect.

In a preferred embodiment of the invention, the dentifrice is in the form of a paste, and in this event it will sugars and honey can also be employed. As binders there can be used carboxymethylcellulose, gum tragacanth, sodium alginate, Irish moss, gum acacia, pectin, etc. Those skilled in the dentifrice art will know other carriers, softeners and binders The pastes may be either of the aqueous type containing substantial amounts of water (above 18%), or of the substantially anhydrous type, containing less than 5% water Formulations are given below for both types.

In addition to pastes the dentifrices of the invention may be in the form of powders or liquids. The main difference between a paste and powder is that the latter contains little or no water and usually no binder or softener. A liquid usually differs from a paste in that it is more fluid and it contains no solid polishing agent.

The following are general formulations of tooth pastes, powders and liquids of the type contemplated according to the present invention (parts are expressed in terms of parts by weight):

Aqueous Tooth Paste Parts by weight Organic phosphate 0.05 to 2.0 Water 18 to 25 Binder 0.8 to 1.2 Polishing agent 40 to 50 Softener or humectant 20 to 25 Detergent to 2 Sweetener 0.1 to 0.2 Flavoring oils 0.9 to 1.2

Substantially Anhydrous Tooth Paste Parts by weight Organic phosphate 0.05 to 2.0 Water 0 to 4.5 Binder 0.3 to 1.2 Polishing agent 45 to 70 Humectant 25 to 45 Detergent 0 to 2 Sweetener 0.03 to 0.10 Flavoring oils 0.9 to 1.2

Powder Parts by weight Organic phosphate 0.05 to 2.0 Polishing agent 93.6 to 98 Detergent 1 to 3 Flavoring oils 0.85 to 1.2 Sweetener 0.1 to 0.2

Liquid Parts by weight Organic phosphate 0.05 to 2.0 Water 60.1 to 92 Detergent 1.5 to 5 Softener 5 to 30 Binder or suspending agent 0.5 to 1.5 Flavoring agent 0.85 to 1.2 Sweetener 0.1 to 0.2

In order more clearly to disclose the nature of the present invention, specific examples illustrating the preparation of typical dentifrices will hereinafter be described. It should be understood, however, that this is done solely by way of example and is intended neither to delineate the scope of the invention nor limit the ambit of the appended claims. Unless otherwise stated, quantities of materials are referred to in terms of parts by weight. The materials are mixed together in accordance with the standard practices in the dentifrice art.

4 EXAMPLE I The following is an example of a series of tooth paste formulations:

Ingredient A B Dlsodium-mono-lauryl orthophosphate Monosodlum-di-lauryl orthophosphate Deionized water Soluble saceharim...

Carboxymethylccllulose (HV120) Dicalcium phosphate Sorbitol Flavoring oils EXAMPLE II The following is an example of a series of tooth paste formulations Ingredient A B Dlsodium-mono-stearyl orthophosphate Monosodium-di-stearyl orthophosphate 1. Delonlzed water 22. 22. 90 Soluble saccharlmm 0.15 0. 15 Carboxymethyleellu 1. 0 1. 0

Dicalcium phosphate 50.0 50.0

Sorbitol 23. 05 23. 05 Flavoring oils 1.10 1.10

EXAMPLE III The following is an example of a series of tooth paste formulations:

(FOOTNOTE.-The mixed phosphates comprise a mixture of about 42% of disodium-mono-lauryl orthophosphate, 54% of monosodlum-tll-lauryl orthuphosphate, 3% tri-lauryl orthophosphate, and about 1% tree orthophosphoric acid.)

EXAMPLE IV The following is an example of a tooth paste formulation which is relatively anhydrous, i.e., having less than 5% water:

Ingredient: Parts by weight Mixed orthophosphates (same mixture employed as in Example 111 above) 1.55 Water, deionized 4.35 Glycerin U.S.P. 41.0 Saccharin, soluble U.S.P. 0.05 Carboxymethylcellulose (HV-l20) 0.50 Dicalcium phosphate 50.85 Sodium lauryl sulfate 1.80

Flavoring oils EXAMPLE V The following is an example of a series of tooth powder formulations Ingredient A 13 Mixed orthophosphates (same mixture employed as in Example III above) 1. 8 1. 5 Dicalcium phosphate 95. 5 95. 5 Polyoxyethylene sorbltan 1. 5 2 Soluble saceharin 0.15 0.15

Flavoring oils EXAMPLE v1 The following is an example of a series of liquid dentifrice formulations:

Ingredient The terms and expressions employed are used as terms of description and not of limitation, and it is not intended, in the use of such terms and expressions, to exclude any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed.

What is claimed is:

1. A dentifrice comprising a dentifrice vehicle and at least about 0.05% by weight of an organic phosphate of the formula:

wherein R is a member selected from the class consisting of a benzyl group, an alkyl group containing from 1 to 24 carbon atoms, inclusive, R and R are members selected from the class consisting of hydrogen, an alkyl group containing from 1 to 24 carbon atoms, inclusive, a benzyl group, an alkali-metal ion and an ammonium ion, provided that when R and R are not a member selected from the class consisting of alkyl and benzyl groups and R is an alkyl group, R shall contain at least 7 carbon atoms.

2. A dentrifice in accordance with claim *1, in which the vehicle is a paste.

3. A dentrifice in accordance with claim 1, in which the vehicle is a powder.

4. A dentrifice in accordance with claim 1, in which the vehicle is a liquid.

5. A dentrifice in accordance with claim 1, which also contains a polishing agent.

6. A dentrifice in accordance with claim 1, which also contains a surface tension depressant.

7. A dentrifice in accordance with claim 6, wherein the surface tension depressant is a synthetic detergent.

8. A dentrifice in accordance with claim 1, which also contains a binder.

9. A dentrifice in accordance with claim 1, wherein the organic phosphate is di-sodium-mono-lauryl orthophosphate.

10. A dentrifice in accordance with claim 1, wherein the organic phosphate is mono-sodium-di-lauryl orthophosphate.

11. A dentrifice in accordance with claim 1, wherein the organic phosphate is di-sodiurn-mono-stearyl orthophosphate.

12. A dentrifice in accordance with claim 1, wherein the organic phosphate is mono-sodium-di-stearyl orthophosphate.

References Cited in the file of this patent UNITED STATES PATENTS 2,586,897 Woodstock Feb. 26, 1952 2,689,170 King Sept. 14, 1954 2,757,125 Mudrak July 3-1, 1956 2,759,975 Chiddix et a1 Aug. 21, 1956 2,772,203 Salzmann Nov. 27, 1956 OTHER REFERENCES Chem. Abstr., vol. 47 (1953), p. 11223d.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent. No. 2,955,984 October 11, 1960 Michael Gabriel Buonocore et al.

It is hereby certified that error appears in the-printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 2, line 49, for "oelylv' read oleyl column 3, line 8, after "water" insert a periodgccolumn- 6, lines 1, 3, 5,

7 9, ll, 13, l5, 18, 21 and 24, claims 2 through 12, inclusive for "dentriiice", each occurrence, read dentifrice Signed and sealed this 11th day of April 1961.

(SEAL) Attest: ERNEST W. SWIDER ARTHUR W. CROCKER Attesting Officer Acting Commissioner of Patents 

1. A DENTIFRICE COMPRISING A DENTIFRICE VEHICLE AND AT LEAST ABOUT 0.05% BY WEIGHT OF AN ORGANIC PHOSPHATE OF THE FORMULA: 